In the work, porous silicon with observed photoluminescence was made from a p-type silicon substrate doped with boron and crystallographic orientation (100) using the method of electrochemical etching in a solution containing H2(SiF6) (silicon hydrofluoric acid) and ethyl alcohol. Thin carbon films were sprayed by high-frequency magnetron sputtering at room temperature onto the surface of porous silicon. The resulting carbon-doped thin films of porous silicon were irradiated on a pulsed electron booster and comparisons were made with nonirradiated films of porous silicon. To understand the effect of carbon on the properties of porous silicon films samples were analyzed by Raman spectroscopy, spectrophotometry, and scanning probe microscopy (SPM). The results of the SPM showed that the roughness of the samples increases after carbon doping on the surface of porous silicon. Thus, for the first time, experimental results were obtained on the effect of irradiation on carbon-doped porous silicon obtained in a solution containing hydrogen hexafluorosilicate H2(SiF6) and a significant change in its optical properties was shown. The results of the study showed that irradiated samples of carbon-doped porous silicon have better photoluminescence compared to nonirradiated samples.